Treatment of wool-containing textile materials and products thereof



Patented Aug. 12, 1952 UNITED T E PATENT F E,

TEXTILE MATERIALS AND UCTS THEREOF PROD- John G. Erickson, Greenwich, and Walter M.

Thomas, ,Springdale, Conn., assignors to American Cyanamid'Company, New York, N'. Y., a

corporation of Maine No Drawing, Application September 28, 1949,

Serial No. 118,456

l This invention relates to the treatment of protein-containing textile materials and to the products thereof. More particularly the invention is concerned with a process of treating protein-containing textile materials, for example wool and wool-containing fabric and other textile. mate- 13 Claims. (Cl. 8-115.6)

rials, to impart improved properties thereto by -(a) and up to about 97% of a comonomer which is different from the-compound of (a), which is copolymerizable therewith and which contains a single "CHz=C grouping, e. g., ethyl acrylate, styrene, acrylonitrile, etc. .The monomericl compounds embraced by the aforementioned general formula are glycidyl acrylate, glycidyl methacrylate' and glycidyl crotonate. The resulting impregnated textile material is then suitably treated, as by heating (e. g., at a temperature within the range of from about 200 F. to about 425 F. under atmospheric pressure, orwith steam under superatmospheric pressure), to; cure the said polymerization product substantially completely. The cured polymerization product 'is substantially water-insoluble. The scopeyof the invention alsoincludes the products obtainedby treating the textile material. p l Protein-containing textile materials, for instance wool-containing textile materials such as loose wool itself and yarns, threads and woven,

2.2%. wool in" untreated state showed a shrinkageof A number of different bethods have been,proposed for the treatment of textile materials formed of or containing wool or-otherprotein fibers in order to prevent or decrease felting and shrinking. In many cases such reduction ,in felting and shrinking tendencies has been obtained 7 at the sacrifice-of some other desirable property of the material. I Some treatments damage the fiber and reduce the wearing qualities while other impart an undesirable harshness to the fabric. Other treatments are not permanently eifective and may even cause an ultimate increase in shrinkage. Still othershrink-proofing methods'are diificult to apply with uniformity and create hazards to the workers involved in their applications. I

The present invention is based on our discovery that protein-containing textile materials, e. g., wool and wool-containing textile materials, when treated with -apolymerizable' substance of the kind described in the first paragraph of this specification yield a treated material which has 'excellent-shrinkageresistance, a soft feelingto 'the'touch '(tha't is,a"g'ood hand a permanent and improved finish which-remains after laundering, and-usually an increased tensile strength 'as compared'with the untreated material. For example, when anaqueous emulsion ofa reactive copolymer of, by weight,'45 parts. of ethyl acrylate and 5 part of glycidyl methacrylate was applied to a piece of woolen goods and the tr-eatedgoods, after being framed and air-dried, was cured by placing the impregnated cloth first in a steam pressure chamber for 5 minutes at about 240 F., followed by heating at atmospheric pressure-,in an air oven for 6' minutes; at about, 400 F., the treated woolenmaterialhad a soft hand, a substantially permanent finish and even. after five launderings (la-minutes eachin soap solution followed by drying) "showed a. shrinkage ofgonly In marke contrast, the same kind of approximately 17 when similarly laundered.

felted and knitted cloth composed of or containing wool have a very undesirable tendency to felt and shrink when subjected toordinary washing operations. The tendency of these proteincontaining textile materials to felt and shrink is generally due to curling and intertwining of the protein fibers asthe fabrics are matted and subjected to the mechanical movements. of the washing process. As a result, the textile material becomes more closely compacted, thicker and has a considerably reduced area.

Similar results also are obtained with glycidyl methacryla-te alone, as well as with other unsaturated glycidyl esters used in practicing the present' invention, -'i'n monomeric or reactive polymeric (reactive partly polymerized): state and also-with Other reactive copolymers of the kindbriefly described in the first paragraphof-this specification and more fully hereafter. Itwas'quite. 1111- expected and unpredictable that monomericgl'ycidyl esterstand'reactive polymers and copolymers thereof, such as 'are' used in carryingiour invention into effect, would impart such improved shrinkage resistance to a. protein-containingtex- 3 tile material, specifically a woolen fabric. It also was quite surprising and unexpected that this shrinkage resistance would be imparted to' the woolen goods without materially lessening its softness to the touch.

By employing the textile-treating agents of the kind with which this inventionis concerned,

it i possible to obtain equally as good or better control of the shrinkage of, for example, wool than is possible by the use of conventional treating agents. Another advantage flowing from our invention is that, if desired,a somewhat lesser' amount of treating agent may be employed than is customarily required in the treatment of a protein-containing textile with most conventional 'oi'any two or all three of the reactive homopolymers of the said glycidyl compounds in any proportions) or With a reactive, partly polymerized product of polymerization of a polymerizable composition comprising, preferably, at least about 3% by weight thereof of glycidyl acrylate, methacrylate or crotonate (or mixture thereof in any proportions), but preferably glycidyl methacrylate alone, and the remaning comonomer (or ctextile-treating agents in order to render them re-' sistant to shrinkage and creasing. For instance;

in the case of wool'as much as about 16%, by

weight of the wool, or a conventional treating agent may be required in order to obtain'satisfactory shrinkage and crease control of the woolen fabric, whereas with the 'polymeriz able substances used in practicing the present in ention satisfactory results usually are obtained with, by weight, about 8 or or less of the polymerizable substance; based on the weight of the dry, untreated wool. The use of higher amounts, however, for example as much as'15 or 2O by weight of the dry, untreated material, or even higher (e. g., or of the polymerizablesubstance'is not precluded and in some cases even may be desirable, for instance when itis desired to produce a weighted protein-containingjabric. Still another advantage accruing from on inventio as compared with the polymeric and copolymeric isocyanate compositions; which heretofore have been employed or suggestedfor use-in efiecting shrinkagecon'trol o'favoolen and other fabric materials, is that the monomers and reactive polymers and copolymers; used; in practicing: the present invention are non-reactive withwater, in which respect they are unlike the isocyanates. Hence our textileetreatin agents can be readfly applied in emulsified or dispersed state toth'e textile to be treated, with, obvious advantages as comparediwith thetuse of an inert, organic solvent which is commonly required applying an isocyanate composition to a textile which is to be rendered resistant to shrinking. 1 r "The unsaturated glycidyl compounds in practicing the present invention, that is, glycidyl acrylate, glycidyl methacrylate and g ycidyl crotonate, are polymerizable materials that can be caused topolymerize either thro gh the ethylenically unsaturated grouping of the compound; or, by suitableichoice of a catalyst, primarily through the epoxy grouping; or, through both the unsaturated linkage and the epoxy grouping. These monomers and polymers thereof are more ful y I described in the copending application of one of us "(John G. Erickson), Serial No, 3i,142, fifled June '19, 1948, now Patent No. 2,556,075,,dated June 5,1951, wherein also are described methods for their preparation. broadly embracing those which are used in practicing our invention are more fully described and a particular speciesis claimed in our copending Reactive copolymers application Serial No. 34,143, also filed June 19,

-1948,:now Patent Nq. 2 ,5' s0,9c1, dated Januaryl,

glycidyl acrylate, methacrylate or" crotonate '(o'r a mixture of any two or' all three ofthese monomonomers) being a compound (or compounds) contains a single CH2=C grouping.

I ilustrative examples of monomeric materials which can be copolymerized with the unsaturated glycidyl esters hereinbefore described to produce reactive copolymers that can be usedin practicing the present invention are N-dialkyl acrylamidese. N-dimethyl, -cliethyl, -dipropyl, -dibutyl," -diamyl -dihexyl, ,-dioctyl, etc., acryla-mides; the acrylic; alpha-alkyl acrylic and alpha-haloacrylic esters ofsaturated monohydric alcohols, for instance saturated aliphatic monohydric alcohols, .e."g., the methyl, ethyl, propyl, isopropyl, vbutyl, isobutyl, amyl, etc., esters of acrylic, ,methacry'lic, ethacrylic, propa'crylic, chloro'acrylic, bromoacrylic, etc., acids; the phenyl," benzyl, phenylethyl, etc., esters of the aforementioned acids; vinyl aromatic compounds, e. g., styrene, alpha-methyl styrene, dimethylstyrenes, dichlorostyrenes, the various cyanostyrenes, the variou methoxystyrenes, vinyl naphthalenes, etc.; vinyl and vinylidene halides, e. g, vinyl and vinylidene chlorides, bromides, etc. -all yl vinyl ketones, e. g.,' methyl vinyl lretone, ethyl vinyl ketone, methyl isopropenyl ketone, etc.; itaconic 'diesters "containing a sin- :gle CHZVV=4C grouping, e. g., the dimethyl, diethyl, dipropyl, dibutyh'and other saturated aliphtic monohydric alcohol 'diesters of itaconic acidg'diphenyl-itaconate, dibenzyl itaconate, (ii-(phenylethylkitaconata'eta; vinyl, allyl and metallyl esters of saturated aliphatic monocarboxylic BJ CIdS e. g, Vinyl, allyl and metallyl acetates, v nyl, Y allyl' and -metallyl propionates, vinyl; allyl andmethallyl' v'alerates', etcJ; vinylthiophene; v nyl pyridine'; vinyl pyrrole; nitriles containing asingle CH2=C grouping, e; g.,;acrylonitrile, methacrylonitrile, etc. Other examples of cornonomerscontaining a singleCHz=C groupmg which can'b'e used-in preparing the reactive copolymers that are employed in practicing the present invention are given in, for example, our a liarfnentioned copendingrapplication Serial No. a

Mixtures of the aforementioned monomeric materials can be employed, if desired, as comonomore with the glycidyl ester (or mixture of glycidyl esters), as well as mixtures. of such monomer 'or'm'onom'ers with other copolymerizablematerials containing a single CH'z=C grouping. In cases where the-glycidyl ester and other monomer are not copolym'erizable or are copolyimeriaable only with difficulty in a two-component system, athird monomer can be added so as to obtain acoinpatible, homogeneous mass of copolyrnerizable ingredients;

- Compositions which are particularly useful 5, ontaining,-byweight, (1) from about 3% to about 50% of a'glycidyl ester of the kind aforementioned (e. g., glycidyl-methacrylate or glycidyl acrylate;--and preferably-the former) more particularly from about 5 or to about 25-or 30% of such an ester, and (2) from about 97% to about 50 more particularly from about 90 or- 95 to about 70 or 75%, of an acrylic compound (e. g., ethyl acrylate or other lower alkylacrylate), or amonovinyl aromatic compound (e. g., styrene), or a mixture thereof in any proportions, which compound (or compounds) 1 is copolymerizable with the glycidyl ester and which contains a single CH2=C grouping. Upon treating the woolor-other protein-containing textile as hereindescribed, the reactive polymerization product is cured in situ to yield a substantially waterinsoluble composition with which the finished textile is impregnated.

The polymerizable substances used in practicing our invention, and which contain as an essential ingredient glycidyl acrylate, glycidyl methacrylate or glycidyl crotonate, or any two or all three of these glycidyl esters, may be polymerized by any suitable method. Polymerization (homopolymerization or copolymerization) will often proceed'merely by allowing the material to stand fora prolonged period, c. g., from 4 to 12- weeks or longer, at room temperature (20 to 30 C.).. The homopolymerization or copolymerization is accelerated, for instance, by heating the monomer or mixture of monomers, e. g., at temperatures up to and including the boiling point of the same at atmospheric pressure, using reflux conditions or a pressure slightly above atmospheric if polymerization is effected at the boiling'point oi the monomer or monomeric'mixture. Polymerization" can be effected, if desired, at'superatmospheric pressures ranging, for example, from 5 to 40 pounds per square inch above atmospheric, in which case the temperature of polymerization isslightly above the boiling point of the monomer or monomeric mixture.

Light also may be used to effect homopolymerization of the monomer, or copolymerization between the copolymerizable ingredients of the polymerizable compositions of this invention, although the rate of homopolymerization or copolymerization by this means is relatively slow. Ultraviolet light is more effective than ordinary light. A combination of heat and light usually causes more rapid homopolymerization or copolymerization than light alone.

If desired, the polymerizable composition may be polymerized in emulsion or in solution state. In, the latter case, various inert organic solvents may be employed, e. g., toluene, xylene, dioxane, ,ethersKe. g., dibutyl ether), esters (e. g., butyl acetate), .chlorob'enzene, ethylene dichloride. ketones (e. g., methyl ethyl ketone), tertiary alcohols, v:for instance tertiary-'butyl alcohol,'ter tiary-amyl'alcohol, tertiary-hexyl alcohol, etc., as well'as others. When the reaction is effected solution state, then a temperature at or approaching the boiling temperature of the solution generally is used.

j The polymerization also can be effected by -conventional bulk polymerization technique, in thejpresence or absence of a solvent capable of "dissolving the monomeric material (homomonomer or mixture of monomers) and in which the latterpre'ferablyis inert; or in solution in a -solv'e'nt'in'which-the monomeric materialis solub'l'e but the" polymerization product (polymer or copolymery is insoluble; or. by conventional bead polymerization methods. .Ihe: polymerization. of the monomer or mixture.ofrmo'nomers carixbe efiected by a continuous-processes wellflaslby. a batch operation. Thus the homomonomer:.:-or' monomeric mixture containinglattrace oiicatajlyst may be passed through a conduit with al-. ternate hot andcoolzones;

The homopolymerization of. the? glycidylpester (or esters) or its copolymerization withanother copolymerizable comonomer containing a single cin =c groupin or "with a plurality (e. g., two, three," fouror any desired number "depend ing, for instance, uponthe particular properties desired in'the end'pro'du'ct) of such" comonomer's which are compatible and copolymerizable with the glycidyl ester, is preferablyacceleratedj by incorporating a single 'or' a plurality of polymerization catalysts in theimonoiner or mixture of monomers; "Thepolymerizatioiijcatalystmay be sochosenias to cause the homopolymerization or copolymerization to proceed" wholly or; mainly through the ethylenically unsaturated grouping of the glycidyl ester in the case of homopolymerization or of the said ester and comonomer in the case of copolymerization. In this ,wa there is produced a reactive 'polymer or copoly-' mer which then can be caused to "polymerize further through opening up'o'f the epoxy group ings which are present therein. If desired, partial homopolymerization or .copolymerization'of the polymerizable ingredient or ingredients may be effected with the aid of one polymerization catalyst (e. g., a peroxide 'and,'more' particularly, an organic peroxide catalyst) .an'd polymeriza tion then completed with theaid off a catalyst capable of, opening up the'epoxy groupings, 'efgp, stannic chloride, etc. j]

v Any of the polymerization catalysts which are suitable for use inpolymerizingpompounds containing an ethylenicallyfunsatur'ated grouping, specifically a vinyl grouping,f can be employed. Among such' catalysts are the inorganic peroxides, e. g., hydrogen peroxide, barium peroxide, magnesium peroxide, etc., and the various or ganic peroxy catalysts, illustrative examples of which latter are: the dialkyl peroxide's, efigy, diethyl peroxide, dipropyl peroxide, dilauryli peroxide, dioleyl peroxide, distearyl peroxide,"di5(tert. butyl) peroxide and di-(tert.- amyl) peroxide, such peroxides often beingv designated as" ethyl,

propyl, lauryl, oleyLstearyI, tertbiltyl jarid tertl amyl peroxides; the alkyl hydrogen peroxides, e. g., tert.-butyl hydrogen'peroxid"(ter. ,ebutyi hydroperoxide) tert.-amyl hydrogen peroxide (tert.-amyl hydroperoxide), etc.; symmetrical diacyl peroxides, for instance peroxides which commonly are known under such names as acetyl peroxide, propionyl peroxide, lauroyl peroxide, stearoyl peroxide, malonyl peroxide, succinyl peroxide, phthaloyl peroxide, :benzoyl peroxide, etc.; fattyoil acid peroxides, e. g., coconut oil acid peroxides, etc. unsymmetrical or mixed diacyl peroxides, e. g., acetyl benzoyl peroxide, propionyl benzoyl peroxide, etc.; terpene oxides, e. g. ascaridole, etc.; and salts of inorganic peracids, e. g., ammonium persulfate, sodium persulfate, potassium persulfate, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium perphos- .phate, 1 potassium perphosphate, etc.

Other examples of organic peroxide catalysts that can be employed are-the following:

Tetralin hydroperoxide ,Trt. butyl diperphthalate lycidyl ester;

7. Cumenehydroperoxide 'I'ert.-butylperbenzoatev t 1 2:,4-dichlorobenzoyl peroxide Ureaperoxide. Caprylyl peroxide J; p-Chlorobenzoyl peroxide. 2,2-bis(tert.-butyl peroxylbutane Hydroxyheptyl peroxide. 1 Diperoxide-ofbenzaldehyde Other so-called free; radical types of catalysts, e; g., azoisobutyronitril'e (af-bis-azoisobutyronitrile'), also can be used to accelerate polymerization mainly through the ethylenically unsaturated'grouping. Oxygen also "can be employed as a polymerizationcatalyst or accelerator. x m e f ysts whi h cel ra rolr merization primarily by opening up of the e'poxy grouping of the 'glycidyl ester are: p-toluene sulionic acid,'sulfu ricacid, phosphoric acid, "aluminum chloride, stannic chloride, ferric chloride, boron trifluoride, boron trifluoride-ethyl: ether complex, iodine, etc. i I

The concentration of the catalyst employed is usually small, that is, for the preferred catalysts from, by weight, about 0.5 or 1 part of catalyst per thousand parts of the polymerizable composition to be polymerized to about 3 or 4- parts of catalyst per 100 parts of the monomer or mixture of comonomers. If an inhibitor of the kindherein'after mentioned be present, up to- '6 or 7%. or even more, based on the weight of the polymerizable composition, may be necessary according to the concentration or the inhibitor.

When polymerization of' the polymerizable compositions employed in practicing'our invention takes place in the absence of iapoly'nierizafluoride etherate, etcqare" more orless specific toward polymerization through theyepoxy groupings'. and are believed not to affect the double bjohd'in the unsaturated ester grouping of the The temperature of; polymerization of the polymerizable composition, at atmospheric or slightly above atmospheric pressure and in the presence or absence of apolymeriz'ation catalyst,

can be varied-over a wide range lup to and including or siigh-tly above the boiling point (at atmospheric pressure) "of the monomeric substance as previously has been more fully 'described, but in allcases is below the decomposition temperature of the monomeric material or materials. In most cases the'pol-ymerization temperature will be within the range oi C. to 150 C., more particularly within'the-range of C5 or C; (ordinary room temperature) to 130 C., dependingupon. the particular monomer or mixture of comononierseniployed-g the particular catalyst, ifany, used ,'the-rapidity of polymerization wanted, "and othenmfiuencing factors.-' With certain catalystaimore particularly strong acidic polymeric ion catalysts such, for instance, as gaseous borq t -ri f luoric le, boron triiluoride-ethyl ether complex, concentrated sulfuric acid, anhydrous aluminum chloride, etc. a,

substantially lower polymerization temperature often advantageously may be used, e. g., temperatures ranging between C. and- Q C. or 10 C. At the lower temperatures below the solidification point of the homomonomer or monomeric mixture (or components thereof), polymerization is eiiected while the monomer or mixture of monomers is dissolved or dispersed in a solvent or dispersion medium which is liquid at the temperature of polymerization. Or,fif desired, the monomer or monomeric mixture, that is, the polymerizable composition, be polymerized in dissolved or dispersed state; at temperatures above its solidification point or above the solidification point of the polymerizable components thereof.- The homopolymer or copolymer can be separated from the liquid medium in which ho-mopolymerization or copolymerization was effected by any suitable means, e. g., by filtration, centrifuging, solvent extraction, etc. i

In some cases it may be desirable to incorporate into the polymerizable composition an inhibitor which is adapted toinhibit homopolymerizatlon or copolymerization through the ethylenically unsaturated grouping of the individual monomer or monomers present in the composition. When it is desired to use the inhibitor-modified composition, a catalyst is added in an amount sufficient to promote the polymerization reaction and to yield a polymer or copolymer. Any suit-. able inhibitor of the aforementioned. type or kind can be used, e. g., phenyl-a-naphthylamine, N ,N -di-2-naphthyl-p -phenylenediam-ine, certain cupric salts, e. g., cupric acetate, etc. The amount of the polymerization inhibitor may be considerably varied, but ordinarily it is employed in an amountnot exceeding 3%, generally, less than 1%, by weightof the monomer or mixture of comonomers, e. g., from 0.01% to 0.5% or 0.6% by weight thereof.

The monomeric or the reactive polymeric or copolymeric composition may be applied to the protein-containing textile material in any, suit,- able manner. The textile. material may be contacted with the liquid. monomer or with the polymer or copolymer in undiluted state, or the reactive polymer or copolymer may be applied in. the form. of a solution or dispersion thereof. In all cases the amount of, treating agent which isdeposited'or incorporated in the protein-containing textile material, e. g., wool or a, woolcontaining textile material; is at least about 1% by weight, based on the dry weight of the textile material. The amount will vary depending, for instance, upon the particular protein-containing textile material. that is-un'dergoing treatment, the. particular monomer, polymer or copolymer employed, the kind of emulsifying'agent used (e. g., anionic, cationic or non ionic), it applied from an emulsion or'dispersion, whetherornot a. weighted textile is. desired, etc." Ordinarily, however, the. amount of polymer, or copolymer that is incorporated in. the finished. textile material is from about 2% to about 15%, more particularly from. about 5% to about10'%,.by weight of the dry, untreatedmaterial, but if a. weighted textile iswanted it may. be much more, for exampleaas much as about 30% or more by weight of the dry, untreated textile. If desired, an initial or an additional amount of catalyst advantageously; can be incorporated into thetextiletreatingz composition comprising the undissolvedt .or 'undispersed monomer or; a

solution or aqueous dispersion or an aqueousorganic solvent dispersion of the monomer, or reactive polymer or copolymer, prior to treating the textile material. Suchcatalysts may be the same or different from those used in preparing the reactive polymer or copolymer (partial polymer or copolymer), and. the amount of catalyst employed may be of the same order oreither more or less, 'e. g., from 0.005 to 6%, more particularly from 0.05 .-to by weight of. the polymerizable substance.

In the textile material to be treated contains fats, oils or other contaminants, it is first thoroughly cleaned in any suitable manner prior to treatment with the polymerizable substance. Y

Various methods may be employed in applying the treating'compositions. For example, the dry textile material may be immersed in the liquid composition and then passed through suitable rolls, as in a padder or mangle, to insure uniform impregnation and to remove excess treating agent. However, the textile material also may be impregnated or coated and impregnated by other methods, for example, by spraying or brushing the liquid monomer or asolution or dispersion of the monomer or reactive-polymer or copolymer upon the textile or byxapplyirig thereto a liquid reactive. polymer or copolymer in undiluted state. Or, the solid, thermoplastic, reactive polymer or copolymer itself may be combined with the textile material as by passing a sheet or cloth of thesame, having thereon or therein the said polymer or copolymer'in finely divided state, between hot rolls. The'impregnating operation and the degree of impregnation are adjusted so that the amount of monomer, polymer or copolymer which is'tak'en up by the textile material will be most effective and economical in producing the desired. results.

If the reactive polymer or copolymer has been applied in dissolved or dispersed state to the textile material, the treated textile is heated to volatilize the inert, volatile organic liquid (if :the polymer or copolymer was applied as a solution thereof), or to volatilize the water (if the polymer or copolymer was applied as an aqueous dispersion thereof), or to volatilize the water and the inert organic liquid (if the polymer or copolymer was applied in the form of 'an inert organic liquid-Water dispersion) and, also, to

convert in situ the reactive polymer or copolymer to a substantially completely cured condition, in which form it is substantially water-insoluble. It will be understood, of course, that when the monomer is applied to the textile, -e. g., in undissolved state or in the form-of a solution'or dispersion, it too is converted in situ to a" substantially completely cured or polymerized state, in which state it is substantially water-insoluble, that is, it is practically unaffected by water. The cured polymers and copolymers, which are formed in situ, also are insoluble or substantially insoluble in conventional organic solvents, e.'g., toluene, xylene, alcohols (ethanol,'etc.), carbon tetrachloride, ethers and others Any suitable elevated temperature maybe employed, but in no case should the temperature be so high as to char or otherwise detrimentally affect the textile material. most protein-containing textiles temperatures within the range of from about 200 F. to about 425 may be used satisfactorily.- firdinarily; temperatures at or slightly above the boiling point ot-water or of the particular inert organic liquid (e. g., diethyl ether, etc.);,-,

For instance, with v:10 solvent employed (ifany) are suflicient to effect the desired result. Of course, it will be understood by those skilled in the art that there is a time-temp eraturerelationship involved; the lower the temperature the longer the time of heating, and the higher the temperature the shorter the heating period. The temperature also will vary somewhat with, for instance, the particular protein-containing textile which has been treated and the particular monomer, polymer or copolymer employed.) Steam treatment under superatmospheric pressure, e. g., at steam pressures corresponding to temperatures of from 220 F. to 350 F., alsocan be used'alone' or in conjunction with a heat treatment in air at atmospheric pressure to polymerizethemonomer or reactive polymer or copolymer to a cured or waterinsoluble state. v

After the textile'materi'al, e. g., woolen jfa'bric material, has been treated as hereinb'efor'egdejscribed, it may be given, if desired or necessary, a mild soaping for asshort period before finishing. The textile material then may be given the usual finishingtreatments required in a particularcase,

.e. g., decatizing, brushing, shearing, pressing, etc.

In order that those skilled in the art better may understand how the presentinvention can be carried into effect, the following examples are given by way of illustration and notby way of limitation.- All parts and-percentages areby weight. The woolen samples used in obtaining shrinkage data are taken from'the same bolt of woolen fabric.

l j Parts Glycidyl methacrylate Y10.0 Ethyl acrylate (anhydrous) IQ. 90.0 Azoisobutyronitrile (polymerization catalyst); 0.5 Toluene (anhydrous) 100.0

' A solutionxcontaining the glycidyl methacry late, ethyl acrylate'and'80% (0.4 part) oft-he azoisobutyronitrile is added'dropwise'to the boiling, stirred toluene (under reflux) over a, period of about 1 hour. At the end of-this period-the solution. is 'noticeably viscous. After heating under reflux for an additional 2 hours and 50 minute the solution has further increased in viscositygThe remainder (0.1 part) ofthe" am- -isobutyronitrile in'about 21 parts of dry toluene isadded'slowly to the refluxing solution after heating for'an additional 50 minutes. Heating isdiscontinued after a totalperiod of about 7% hours. A portion of the solution is diluted with dry toluene to form a solution of reactive copolymer containing about 10% of copolymer solids.

:A piece of woolen goods (9" x 23", in size) is immersed in the copolymer solution and passed through squeeze rolls. The impregnated wool contains approximately 10% of copolymer solids. The sample is framed, air-dried for a short period and then heated for 6 .minutesat 290-300 F. After cooling to room temperature the sampleis removed from the frame,'allowed to remain undisturbed for about 16 hours andthen'measured prior to laundering. The method of laundering is a modification of the standard method of A. A.;,T. C. C. and involves heating for 20 to 30 minutes at 240 F. while drying after each wash? ing. After a cycle of 5 washing (10- minutes in soap'solution): and drying operations, the treated cloth shows a shrinkage of 11.9% whereas the untreated wool whensimilarly washed shows a shrinkage of 17%.- Another sample of the same EXAMPLE 2- The same formulation and procedure are followed as described under Example 1 with the exception that instead of 10 parts. of glycidyl methacrylate there is used 10 parts of glycidyl acrylate. Similar results are obtained.

EXAMPLE 3 I Same as in Example 1 with the exception that instead of 90 parts of ethyl acrylate there is used 90 parts of n-butyl acrylate. Similar results are obtained.

' EXAMPLE 4 Parts Glycldyl methacrylate 20.0 Ethyl acrylate (anhydrous) 80.0 Azoisobutyronitrile 0.5 Toluene (anhydrous) 100.0

The same general procedure is followed as described under Example 1, the solution of monomore and catalyst in this case being added over a period of 50 minutes. After refluxing for an additional 3 hours and 10 minutes the remainder (0.1 part) of azoisobutyronitrile dissolved in about 8.7 parts of dry toluene is added slowly to the refluxing solution. Heating is discontinued 8 hours after the time when the solution of monomers is first added to the refluxing toluene. The resulting viscous copolymer solution is allowed to cool, after which it is diluted with additional dry toluene to yield a solution containing approxi- -mately,10%- by weight of reactive ccpolymer. This solution is divided into two portions, A and B, which are used in treating woolen goods as described below:

Solution A.This solution is used as is in impregnating a piece of woolen goods as described under Example 1 with the exception that the impregnated cloth, after being 'air-dried'fcr ashort .period, is heated for 6 minutes at 400 F. whereby, as in the prior and subsequent examples, the copolymer is cured (insolubilized) to a substantially water-insoluble condition. The results of shrinkage tests, which are made as described under Example 1, are a follows:"

Per cent shrinkage After washing cycles of minutes each 6.7 After 5 washing cycles of 10 minutes each plus 1 hours additional washing 7.5

'wooien goods as described under Example 1. As

in that example, the air-dried cloth is heated for 63 minutes at 290-300 The results of shrinkage tests on the treated wool are as follows:

Percent shrinkage After 5 washing cycles of 10 minutes each L7 After 5 washing cycles or" 10 minutes each plus 1 hours additional Washing 5.6

EXA'IWPLE 5 The same formulation and procedure are followed as described under Example 4 with the exception that instead of 20 parts of 'glycidyl methacryltae there is used 20 parts of glycidyl crotonate. To the solution of reactive copclymer there is added a small amount of phosphoric acid as described in the precedingv example, and this acid-catalyzed solution is employed in treating woolen cloth as is set forth with reference to use of Solution'B of Example 4. Similar results are obtained.

EXAMPLE 6 Parts Glycidyl methacrylate 5.0 Methyl acrylate 95.0 Benzoyl peroxide (polymerization catalyst) 1.0

Toluene (anhydrous) 100.0

The glycidyl methacrylate and methyl acrylate are copolymerized as described under Example 1, and the resulting solution of reactive copolymer is used in treating woolen cloth likewise as described under that example. Similar results are obtained.

EXAMPLE 7 Parts Glycidyl methacrylate 5.0 Ethyl acrylate 45.0

Water 190.0 25% aqueous solution of di-(Z-ethylhexyl) sodium sulfosuccinate (anionic emulsifying agent) 10.0 30% aqueous hydrogen peroxide 0.55 5% aqueous Nazi-IP04 2.5

are heated together while stirring under reflux in a reaction vessel placed on a steam bath, which vessel is provided with a stirrer, thermometer and reflux condenser. Heating and stirring are continued for 1 hour and 50 minutes, after which the steam is turned off the bath and stirring is continued for an additional 55 minutes. At the end of this period steam is turned into the aqueous reaction mass for 30 minutes to remove most of the residual (unreacted) monomers. The resulting, strained (through cheese cloth), aqueous emulsion of reactive copolymer has a pH of about 45, contains about 15.8% of copolymer solids and is stable for 16 hours and longer. Pieces of woolen cloth are impregnated with this emulsion as described under Example 1. In one case (sample A) the framed, air-dried, impregnated Woolen fabric is heated for 6 minutes at 290-300" F. to cure or insolubilize (render insoluble in water) the reactive copolymer in situ. In another case (sample B) the treated woolen goods, after being framed and air-dried, is cured by placing the impregnated cloth first in a steam pressure chamber for 5 minutes at about 240 F., followed by heating at atmospheric pressure in an air oven for 6 minutes at about 400 F. The treated goods has a soft hand, good tensible strength and a substantially permanent finish. The results of shrinkage tests on the treated samples are as follows:

Percent Shrinkage Sample A Sample B of glycidyl methacrylate. obtained.

. parts of styrene.

I Same asin Examplel with the exception that instead of parts of glycidyl methacrylate there is used 2.5 parts of glycidyl acrylate and 2.5 parts Similar results are EXAMPLE i 1 The same formulation and procedure are followed as described under Example 7 with the exception that instead of 5 parts. of glycidyl methacryltae there is used 1.67 parts of glycidyl 'acrylate,-1.67 parts of glycidyl methacrylate and 1.6? parts of 'glycidyl crotonate. Similar results are obtained. I a

EXAMPL 11 Sameas-in Example 7 with the exception. that instead-of 45 parts of ethyl acrylate there is used .45 parts of styrene; Similarresults are obtained.

XA L 12 I; Thesame formulation and procedure are followed asdescribed underExample 7 with the exception that instead of 5 parts of glycidyl methacrylate there is used parts of this .com-

pound, and instead of 45 parts of ethyl acrylate there is used 35 parts of acrylonitrile. Similar results are obtained. A

g g EXAMPLE 13 1, Same as in Example 7 with the exception that li'nstead of, 5flpa'rts of 'glycidyl 'methacrylate there is'fused 2.5 parts of glycidyl acrylate and 2.5

parts of glycidyl. crotonate, and. insteadof .45 parts of ethyl acrylate there is used 45 parts of methyl m'ethacrylate. Similar results are obtained.

EXAMPLE 14 The same formulation and procedure are followed. as described under Example .7 with the. exception that'instead of 5 parts of ,glycidyl methacrylate there is used 2.5 parts of glycidyl methacrylate and 2.5 parts of glycidyl crotonate, and instead of 45 parts of ethyl acrylate there is used 45 parts of styrene. Similar results are obtained. f 4 1 I EXAMPLE .15

' Same'as in Example? with the exception that instead of 5 parts of glycidyl methacrylate there is used'10 parts of this compound, and instead 1 of 45 parts of ethyl acrylate there is used 40 parts of 2,3-dimethylstyrene. Similar results are obtained.

The same formulation and procedure are fol- "lowed as-des'cribedundel' Example 7 with the exception-that insteadof 5 parts of' gl'ycidyl methacrylate there is used 14 parts of glycidyl acrylate, and instead of 45 parts of ethyl acrylate there is used 18 parts of methyl acrylate and 18 Similar results are obtained.

EXAMP E .1?

Same as in Example '7 with the exception that EXAMPLE 18 Glycidyl methacrylaten 20.0 Methyl. methacrylate 80.0 Azoisobutyronitrile 0.5 Toluene (anhydrous) i 100.0

A solution containing the glycidylmethacrylate, methyl methacrylate and 80% (0.4 part) of the azoisobutyronitrile is added dropwise to ('90 parts) of the boilin'gQstirred-tolune (under reflux) over-a period of about65 minutes. After heating for an additional 2 hours under reflux the solution is very viscous. At this point the remainder (0.1 part) of the azoisobutyronitrile dissolved in the remainder (10 parts) of the toluene is added slowly to the refluxing solution. Heating under reflux at the-boiling temperature ofthe mass is continued for an additional 1 hours, making a total heating period of 6 hours from the time whenthe addition of the catalyzed mixture of monomers to the refluxing toluene is first started. The conversion of monomers to copolymer is approximately 90% of the theoretical.- The solution of reactive copolymer as initially produced is diluted with dry toluene to yield a solution containing about 10% of copolymer solids. Pieces of woolen goods are impregnated with this 10% copolymer solution as described under Example 1. In one case (sampleA),the framed, air-dried, impregnated woolen fabric is heated for 6 minutes at 290-300 F., and in another' case (sample B) for 6 minutes at about 400 F. to cure the reactive copolymer in situ to a substantially water-insoluble:condition; The treated goods has a soft hand and asub'stantially permanent finish even after numerous'launder- "inga I? The-results of shrinkage test's on thetreatg "e'd sa'm'plesare as follows? 1 Percent Shrinkage Sample A Sample} Alter 5 washing'cycles of 10 minues each 10.8

EXAMPLE 19 r Same as in Example 18 with the exception that instead of 0.5 part of azoisobutyronitrile there-is employed 1.0 part of tert.-butyl hydroperoxide,

and instead of parts of anhydrous toluene thereis used 100 parts of anhydrous xylene as the inert liquid medium in which the copolymerization is effected. This solution of reactive copolymer is employed in treating woolen cloth as described under Example 18. Similar results are obtained.

EXAMPLE go EXAMPLE 2i 1 Same s in Example 18 withtnepx cepuonthat insteadof- 80 parts of methyl methacrylate there is used 80 parts-of ethyl methacrylate- Similar resultsare obtained. j

heating period is 12 hours instead of EXAMPLE 23 7 Same as in Example 18 with the exception that insteadof 20 parts of glycidyl methacrylate there is used parts of glycidyl acrylate, 5-parts of 'glycidyl :crotonate and5 parts of glycidyl methacrylataand instead of 80 parts of methyl methacrylate there is employed 425 parts of styrene and 42.5 parts of methyl methacrylate. Similar results are obtained.

A solution containing the glycidyl methacrylate, styrene and 80% (1.6 parts) of the azoisobutyronitrile is added dropwise to 90% (360 parts) of the boiling, stirred toluene (under reflux) over a period of 2 hours and 55 minutes. After heating for an additional 2 hours and 25 minutes the remainder (0.4 part) of the azoiso- ,butyronitrile dissolved in the remainder (40 parts) of. the toluene is added slowly to the refiuxing solution. Heating under reflux is continued'for an additional hour, making a total heating period of 6 hours and 20 minutes from the time when the addition of the catalyzed monomeric mixture to the refluxing toluene is firstI started. The conversion of monomers to copolymer is approximately 85% of the theoretical. A solution of the reactive copolymer in toluene is prepared as described under Example 18, and this solution is applied to woolen goods likewise as described under Example 18. As in Example 18, sample A is the sample which is ,cured by heating the impregnated Woolen piece for 6 minutes at 290-300 F., while sample B is cured by heating the treated cloth for 6 minutes at about 400 F. The treated goods has a good hand and a wash-resistant finish. The results of shrinkage tests on the treated samples are as follows:

Percent Shrinkage Sample A Sample B EXAMPLE 25 Same as in Example 24 with the exception that 320 parts of alpha-methyl-para-methylstyrene is v.used in place of 320 parts of styrene, and the total 6 hours. Similar results are obtained.

EXAMPLE 26 Same as in Example 24 with the exception that 100 parts of glycidyl acrylate is used in place of 80 parts of glycidyl methacrylate, and 300 parts of vinyl acetate is employed in place of 320 parts of styrene. Similar results are obtained.

are obtained. EXAMPLE 2a Same as in Example 24 with the exception that 320 parts of p-methylstyrene is used instead of 320 parts of styrene. Similar results are obtained.

EXAMPLE '29 I JParts Glycidyl methacrylate 80.0 Ethyl acrylate 320.0 Azoisobutyronitrile v2.0 Toluene (anhydrous) 400.0

A solution containing the glycidyl methacrylate, ethylacrylate and (1.6 parts) of the axeisobutyronitrile is added dropwise to (360 parts) of the boiling (under reflux), stirred toluene over a period of 1 hours. Afterheating for 6 hours and 35 minutes from the time when the addition of the catalyzed monomeric mixture to the refluxing toluene is first started, the solution is moderately viscous. The remainder (0A part) of the azoisobutyronitrile dissolved in the remainder (40 parts) of the toluene is now added over a period of about 30 minutes. Heating under reflux is continued for an additional 2% hours. The conversion of monomers to copolymer is approximately 98% of the theoretical. A 10% solution of the reactive copolymer in toluene'is prepared and applied to a piece of woolen cloth as described under Example 18. The reactive copolymer is cured in situ to a substantially water-insoluble state by heating the impregnated goods for 6 minutes at 290-300 F. The treated material has a soft hand, good tensile strength, and a finishwhich remainsjafte'r numerous launderings. After a cycle of '5 washing operations as described .under Example 1, it shows a shrinkage of 8.9% as compared with 17% for the untreated wool.

EXAMPLE 30 Same as in Example 29 with the exception that 320 parts of n-hexyl acrylate is used in place of 320 parts of ethyl acrylate. Similar results are obtained- EXAMPLE 31 Same as in Example 29 with the-exception that instead of 80 parts of glycidyl methacrylate there is used parts of glycidyl aorylate, and instead of 320 parts of ethyl acrylate there is employed 280 parts of the acrylic ester of a'mixture of normal and the various isomeric forms of amyl alcohol. Similar resultsare obtained.

EXAMPLE 32 Same as in Example 29 with the exception that instead of 80 parts of glycidyl methacrylate there is used 40 parts of glycidyl crotonate, and instead of 320 parts of ethyl acrylate there is employed 360 parts of 2,5-dichlorostyrene. Similar results are obtained.

EXAMPLE 33 Same as in Example 29 with the exception that instead of 320 parts of ethyl acrylate there is used 320 parts of p-methoxystyrene. Similar results are obtained.

EXAMPLE 34 A toluene solution of the reactive copolymer of Example 29 containing 10% of copolymer solids is mixed with an equal volume of a toluene solution of a reactive copolymer of, by weight, 90% ethyl acrylate and 10% maleic anhydride, which latter solution also contains 10% of copolymer solids. This solution is applied to a piece of woolen goods as described under Example 18, the treated goods being heated for 6 minutes at 290-300 F. to insolubilize (convert to a waterinsolublestate) the mixture of reactive 'copolymers. The results of shrinkage tests on the treated sampleare as 'follows:'

. Per cent shrinkage After 5 washing cycles of 10 minutes'each--- 6.1 After 5 washing cycles of 10 minuteseach plus 7 1 hours additional Washing 6.4

For the purpose of comparison a piece of the same woolen goods is treated in the same manner with a solution of 10% of the reactive ethyl acrylate-maleic anhydride copolymer alone in are heated together while stirring under reflux in a reaction vessel placed on a steam bath, which vessel isprovided with a stirrer, thermometer and reflux condenser. Heating andstirring are continued for 4 /2 hours, after which stirring is stopped and the emulsion is steamed for 1' hour to remove any unreacted inoricprners.;v The aqueous emulsion is diluted with water to about 10% of copolymer solids, and pieces of woolen goods are impregnated with the diluted emulsion as described under Example 1. In one case (sample A), the framed, air-dried, impregnated woolen fabric is heated for 6 minutes at 290-30051 and in another case (sample B) for 6 minutes at about 400"F. to cure the reactive glycidyl acrylateethyl acrylate copolymer in situ to a substantially water-insoluble condition. The treated fabric has .a soft feeling to the touch and ,a substantially permanent finish. The results of shrinkage tests on the treated samples areas follows:

Percent Shrinkage Sample A Sample B After 5 washing cycles of 10 minutes each 9.4 5. After washing cycles of minutes each plus 7 r 1 hours additional washin g 5. 6

qoesw Solution A Parts Emulsifying agent, specifically a reaction product of 1 moleof octadecyl amine and Water 145.0

' Solution 7 Parts Benzoyl peroxide 0.25

Solutions, A and B arethoroughlymixed and passed twice through a homogenizer, yielding a Per cent shrinkage After 5 washing'cycles of 10 minutes each 4.7 After 5 washing cycles of 10 minutes each plus 1 hours additional washing 5.0

EXAMPLE 37 Same as in Example36 with'the exception that instead of parts of glycidyl methacrylate there is used 50 parts of glycidyl acrylate, and instead of 0.25 .part of benzoylperoxide there is employed 1.5 parts of 30% acetyl peroxide in dimethyl phthalate. Similar results are obtained;

EXAMPLE 38 Same as in Example 36 with the exception that instead of 50 parts of glycidyl methacrylate there is used 50 parts of glycidyl crotonate, and instead of 0.25 part of. benzoyl peroxide there .isemployed 1 part of benzoylperoxideand 0.5 part'oftertbutyl hydroperoxide; also, instead ofcuring the impregnated woolen fabric by. heating it for 6 minutes at 290-300 F., themonomer is polymerized in situ by placing the impregnated goodsfirst in a steam pressure chamber, for 30 minutes at about 240 F.,'followed by heating in an air oven for about 15 minutes atabout 320, F. Similar results are obtained.

EXAMPLE 39 V V Parts Ethyl acrylate -L 180.0 Glycidyl methacrylate 20.0 Ammonium perdisulfate (polymerization catalyst) 0.1 25% aqueous solution of di-(Z-ethylhexyl) sodium sulfosuccinate u 20.0 Water -1.- 580.0

I r !Per cent shrinkage te W i g cycles 01 10 minuteseach 5.6

19 EXAMPLE 40 I Parts Ethyl acrylate 45.0 Glycidylmethacrylate. c1 5.0 Water 197.0 Cetyl dimethyl benzyl ammonium chloride (cationic emulsifying agent) 0.63 30% aqueous hydrogen peroxide (polymerization catalyst) 0.55

The cationic emulsifying agent is first dissolved in a portion of thewater and then diluted with more water. All of the aforementioned ingredients are then heatedt'ogether with stirring under reflux in a reaction vessel placed on a steam bath andprovided with a stirrer, thermometer and reflux condenser.v After refluxing for only about 25 minutes, the copolymerization reaction appears to be almost complete as indicated by the fact that no more ethyl acrylate is refluxing. Heating with stirring on the steam bath isc'ontinued for an additional 2 hours and 35 minutes, after which the emulsion is cooled, filtered through cheese cloth, diluted with water to 10% copolymer solids, and used in treating wool as described under Example 36 using, as in that'example, a -minute cureat 290-300 F. to insolubilize the copolymer in situ. The resultsof shrinkage tests on the treated sample, which has a soft feeling to the touch, are as follows: 7

r Percent shrinkage After washing cycles 'o'f 1 0 minutes each 3.3 After 5 washing cycles of '10 minutes each plus are heatedtogether with stirring for 1 hour under reflux as described under Example40, after which steam is passed throughjthe aqueous emulsion of reactive copolymer for minutes to remove unreacted monomers.

water to 10% copolymer solids, and used in treating woolen goods as described under Examples 36 and 40. The results of shrinkage tests on the treated sample areas follows:

Y ercent shrinkage After 5 washing cycles of 10 minutes each 4.2 After 5 washing cycles of 10 minutes each plus are heated together with 'stirring'for l'h'our and 10 minutes under reflux as described under Example 40, after which steam is passed through the aqueous emulsion of reactive copolymer for minutes to remove unreacted monomers. The emulsion (pH of 6.8) is cooled, filtered through cheese cloth, diluted with water to 10% The emulsion (pH of 6.3) is cooled, filtered through cheesecloth, diluted with copolymer solids-and used-in treating a piece of woolen cloth as described under Examples 36 and 40. The-results of shrinkage tests on the treated sample are as follows:

3 4 Percent shrinkage After 5 washing cycles of 10 minutes each, 4.7 Afterv 5 washing cycles of 10 minutes each plus 1 hoursadditional washings 5.6

Saln'e'as in Example 4 with the exception that, instead of using 20 "parts of .glycidyl methacrylate and parts of ethyl aciylate in forminga reactive copolymer, there is employed parts of glycidyl methacrylate alone 'to yield 'a toluene so luticn of; a reactive polymer. This solution is diluted with dry toluene to approximately 10% polymer concentratiomdivided into two portions, A and B, as in Example 4 and applied to woolen goods likewise as described in that example. Similar results are obtained.

Substantially the same results also are secured when glyc'idyl 'acrylate or crotonate is used in place "of glyci'dyl' methaerylate as described in the precedingparagraph. I

It will be understood, of course, by those skilled in the art that our invention is not limited to the specificre'active copolymers named in the above illustrativeexamples nor to the particular methods of application therein described. Thus, instead of the comonomers specified in the various examples, we canuse any other comonomer or plurality of comonomers that are copolymerizable with glycidyl acrylate, ethacrylate or crotonate and which contain a single CH2=C grouping, numerous examples offwhich have been given hereinbefore and in our copending application Serial No. 34,143, filed June 19, 1948. lllilrewise, polymerization catalysts other than those named in the'variousexamplescan be used, for instance catalysts such-as those previously mentioned by way-of illustration.-

Likewise,jit will beunderstood that our invention is not limited to-theus'e of toluene or xylene as a solvent either in the preparation of the polymeric or copolymeric material or in its application'to-a protein-containing textile material. Illustrative examples of other inert, volatile, organic liquids "(that is, volatile, organic liquids which are non-reactive with the monomeric or partly-polymerized materials), which can be'used -'-in the 'pl'eparation of the treating agent or in applying it to the textile' material in solution state or in the formof an organic liquid-water dispersion arez benzene, dio'xan'e', ethers '(e. g., 'diisop'ropyl ether, dibuty'l ether, etc), esters (e. g., butyl acetate, etc), chlorinated hydrocarbons, for instance carbon tetrachloride, trichloroethylene, ethylene dichloride, chlorobenzones (e. g., 1,3-dichlorobenzene, etc.), and others. If applied in the form of an organic liquidwater dispersion, the organic liquid is one which is immiscible with the water.

If the polymerizable substance (monomeric or reactive polymeric or copolymeric material) is to be applied to the textile material'in the form of an emulsion or dispersion, specifically a water emulsion or dispersion'or an organic liquid-water emulsion or dispersion, any suitable emulsifying or dispersing agent-can be employed, e. g., the sodium salts of the sulfates of a mixture of lauryl and miyristyl alcohols, dioctyl sodium sul- 'iosuccinate, sodium salts of alkylaromatic sulfonic acids (e. g; the sodium saltjof 'isopropylnaphthalene sulfonic acid'), quaternary ammonium salts (e. g., cetyl dimethyl ammonium chloride), etc.

The amount of monomer or reactive polymer or copolymer in a solution or dispersion which is applied to the textile material can be varied considerably, but generally is within the range of, by weight, from about to about 20 or 25% of the solution or dispersion. Good results have beenobtained when the polymerizable substance constitutes about by weight'of the solution or dispersion. ;When solutions or dispersions containin about 10% by weight of monomer or reactive polymer or copolymer are employed, the amount of polymerizable substance which is taken up by the textile undergoing treatment is usually of the order of 8 to 10% by weight of the dry, untreated textile.

Our process can be applied in the treatment of various types of protein-containing textiles, for instance those formed of or containing wool, silk, mohair, fur, leather, regenerated protein fibers or fabrics, e. g., those produced from casein, peanut, corn (zein) egg albumin, feathers (keratin), collagen, etc.; mixtures of such pro- 'tein-containing textiles; and mixtures of such protein-containing textiles with other types of textiles, for instance those formed of cellulose or regenerated cellulose, e. g., cotton, linen, hemp, jute, ramie, sisal, cellulose acetate rayons, cellulose acetate-butyrate rayons, saponified acetate rayons, cuprammonium rayons, etc. In the case of textiles containing mixtures of protein-containing and cellulose-containing fibers, the effect of the treatment is mostly on the former but the latter also may be beneficially effected and may combin therewith. Our process also can be applied in the treatment of colored textile materials as well as whites.

The reason why the aforementioned glycidyl esters and reactive polymers and copolymers thereof have the particular and peculiar property of imparting such outstanding shrinkage resistance to a protein-containing textile material, specifically a wool-containing textile, is not definitely known to us. One mechanism by which the polymerizable substance (monomer or reactive polymer or copolymer) herein described may very likely operate is that which involves the formation of an actual chemical union between the polymerizable substance and the protein-containing substrate, 9. g., wool. For instance, the groups in wool and other proteinaceous material that contain active hydrogen (e. g., NH, -SII, etc.) are thought to react with the epoxy ring to give products which contain groupings such as -Cl-IOHCH2NH. In this way the joining of one fiber to another may be brought about and the tendency to undergo dimensional change may be minimized. A secondary factor contributing to shrinkage control, and which takes place concurrently with the above-mentioned process, appears to be self.- curing of the polymerizable substance on and within the fiber. Thus the finished protein-containing textile material, e. g., woolen fabric material, contains insoluble polymeric or copoly-" meric substance distributedon and within the fibers of the textile. I

The polymerizable substances used in practicing the present invention can undergo polymerization through rupturing of the epoxy ring, leading to cross-linking or conversion to a substantially insoluble state. This rupturing of the epoxy ring seems to proceed when the polymerizable substance is applied to a protein-containing textile, suchas a woolen fabric material, so that the insolubilization or curing of the reactive substance takes place in situ under the influence of heat and/or a polymerization catalyst simultaneously with a chemical'reaction between the treating agent and the proteincontaining textile. As a result, shrinkage resistance of the textile to an outstanding degree is obtained. Furthermore, the treated textile has a soft hand, that is, a soft feeling to the touch, an improved finish and usually increased 'tensile strength as compared with the untreated material. I I

If desired, the treating agents employed in practicing the present invention can be used to supplement or in combination with conventional textile-treating compositions in the treatment of textiles to impart improved properties thereto. i

The terms textile and textile materials as used generally herein and in the appended claims include within their meanings filaments, fibers, threads, yarns, twisted yarns, slivers, rovings, etc, as such or in woven, felted or otherwise formed fabrics. sheets, cloths and the like.

We claim:

1. A process of treating a wool-containing textile material to improve the properties thereof which comprises treating said textile material with a composition comprising ia polymerizable substance selected from the class consisting of (a) monomeric compounds represented by the general formula I R o11=c-o o o Cm-cH-oni With ,and which contains a single CH2=C grouping, and heating the resulting treated material to polymerize the said polymerizable substance to a substantially Water-insoluble state. '2. A process as ,in claim 1 wherein the monomeric compound of (a) is glycidyl methacrylate.

3. A process as in claim 1 wherein the comonomer of (17) is ethyl acrylate.

'4. A process of reducing the felting and shrinking tendencies of a wool-containing textile material which comprises impregnating such a material with an aqueous dispersion containing a reactive, partly. polymerized product of polymerization of a polymerizable composition comprising, by weight, (a) from about 3% to about 50% of a monomer represented by the general where R and R each represents a member of the class consisting of hydrogen and the methyl radical, R representing hydrogen when R represents a methyl radical, and (b) from about 97% to about 50% of a comonomer which is difierent from the monomer of (a), which is copolymerizable therewithand which contains a sinlev CH :Q grouping, the take-up of the said ispersion being such as to; deposit in the textile material at least about 1%. by weight, based on .the dry weight ;of thetextile material, of the said polymerization product, and heating the resulting treated material to volatilize the water and to convert the said polymerization product ,in situ to a water-insoluble condition.

5. A process as in claim 4 wherein the aqueous dispersion also contains a catalyst for accelerating the polymerization of the reactive polymerization. product in situ to a water-insoluble condition.

6. A process as in claim 5 wherein the catalyst is phosphoric acid.

7 A wool-containing textile material impregnated with a substantially water-insoluble composition comprising an insolubilized product vof polymerization of a polymerizable composition comprising, by weight, (a) from about 3% to 100% of a monomeric compound represented by the general formula where R and R each represents a member of the class consisting of hydrogen and the methyl 50% of glycidyl 'methacrylate and from about 97% to about 50% of an acrylic compound which is 'copolymerizable with glycidy-l methacrylate and which contains a single CH2:C grouping.

9. A wool-containing textile material which is resistant to shrinking and which is impregnated with at least about 2%, by Weight of the untreated material, of a substantially water-insoluble composition comprising a cured product of polymerization of a polymerizable mixture containing, by weight, from about 3% to about 50% of glycidyl methacrylate and from about 97% to about 50% of a monovinyl 'aromatic compound which is copolymerizablewith glycidyl methacrylate and which contains asingle CH2=C grouping.

10. The process which comprises impregnating a wool-containing textile material with an aqueous dispersion containing a reactive, partly polymerized product of polymerization of a polymerizable composition comprising, by weight, (a) from about 3% to 100% of a monomer represented by the general formula where R and R, each represents a member of the class consisting of hydrogen and the methyl radical, R representing hydrogen when R representsa methyl radical, and (b) up to about 97% of a comonomer which is difierent from the compound of (a), which is copolymerizable therewith and which contains a single CH2:C grouping; steaming the resulting impregnated textile under a steam pressure corresponding to a temperature of from 220 F. to 350 F.; and heating the steamed textile under atmospheric pressure at a higher temperature ranging up to 425 F., thereby to complete the polymerization of the said polymerization product .in situ to a substantially water-insoluble state.

11. The process of reducing the felting and shrinking tendencies of a wool-containing textile material. which comprises impregnating .said textilematerial with an aqueous dispersion containing a reactive, partly polymerized product of polymerization of a polym'erizable composition comprising, by weight, (a) from about 3% to about 50% of glycidyl methacrylate and (b) fromabout 97% to about 50% of an acrylic compound which is .copolymerizable with glycidyl methacrylate and which contains a single CH2=C grouping; steaming the resulting impregnated textile under a steam pressure correspondingto a temperature of from 220 F. to 350 F.; and heating the steamed textile under atmospheric pressure in air at a higher temperature ranging up to425 F., thereby to complete the polymerization of the said polymerization product in situ to a substantiallywaterinsoluble state.

12. .A process as in claim 11 wherein the acrylic compound of (b) is a lower alkyl ester of acrylic acid.

13. A process as in claim 11 wherein the acrylic compound of (b) is acrylonitrile.

JOHN G. ERICKSON. WALTER M. THOMAS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Powers: Efiect of Synthetic Resins on Cellulose and ProteinFibers, Ind. and Eng. Chem, February 1945, pages 188 to 193. 117-141. 

1. A PROCESS OF TREATING A WOOL-CONTAINING TEXTILE MATERIAL TO IMPROVE THE PROPERTIES THEREOF WHICH COMPRISES TREATING SAID TEXTILE MATERIAL WITH A COMPOSITION COMPRISING A POLYMERIZABLE SUBSTANCE SELECTED FROM THE CLASS CONSISTING OF (A) MONOMERIC COMPOUNDS REPRESENTED BY THE GENERAL FORMULA 